Cadmium- and thorium-containing catalyst

ABSTRACT

A catalyst composition comprising a cadmium component, a thorium component and a support material having acidic properties is disclosed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to a cadmium- and thorium-containingcatalyst and more particularly concerns such catalyst for the reactionbetween hydrogen and a material selected from the group consisting of(a) carbon monoxide, (b) at least one of an alcohol containing from 1 to6 carbon atoms and an olefin containing from 2 to 6 carbon atoms, (c) amixture of an aromatic compound and at least one of carbon monoxide andan alcohol containing from 1 to 6 carbon atoms.

2. Description of the Prior Art

The production from less valuable materials of aliphatic compoundsboiling in the gasoline range, of aromatic compounds, and ofintermediates useful for the production of such aliphatic and aromaticcompounds, is highly desirable and has been the object of several priorart methods involving the use of cadmium-containing catalysts. Forexample, Woodruff et al., U.S. Pat. Nos. 1,625,924 and 1,625,928,disclose a method for producing methanol by reacting oxides of carbonwith hydrogen at high pressures and in the presence of a catalystcomprising one or more non-reducible metal oxides, such as zinc,magnesium, cadmium, chromium, vanadium, or tungsten, and one or moreeasily reducible metal oxides, such as copper, silver, iron, nickel, orcobalt, and a metallic halide. Melaven et al., U.S. Pat. No. 2,301,735,disclose a process for converting heavy hydrocarbon oils into gasolineby contacting the heavy oils with a catalyst comprising silicaimpregnated with a cadmium compound.

Klotz, U.S. Pat. No. 4,269,813, discloses a crystalline borosilicatecatalyst comprising a molecular sieve material having the followingcomposition in terms of mole ratios of oxides:

    0.9+/-0.2M.sub.2/n O:B.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O

wherein M is at least one cation, n is the valence of the cation, y is avalue within the range of 4 to about 600, and z is a value within therange of 0 to about 160, and providing a specific X-ray defractionpattern. M represents an alkali metal cation, an alkaline earth metalcation, an ammonium cation, an alkylammonium cation, a hydrogen cation,a catalytically active metal cation, or mixtures thereof. Klotz alsodiscloses that the original cation "M" in the above formulation can bereplaced by tetraalkylammonium cations, metal ions, ammonium ions,hydrogen ions, and mixtures thereof, particularly hydrogen, rare earthmetals, aluminum, metals of Groups IB, IIB and VIII of the PeriodicTable, noble metals, manganese, and other catalytically-active materialsand metals known to the art. The catalytically-active components can bepresent at concentrations from about 0.05 to about 25 weight percent ofthe crystalline borosilicate. Klotz discloses that the crystallineborosilicate can be employed effectively as a catalyst for variousprocesses including reforming, hydrocracking, transalkylation,disproportionation, isomerization, and alkylation, and is particularlysuitable for the isomerization of xylenes, the conversion ofethylbenzene and the conversion of alcohols, such as methanol, to usefulproducts, such as aromatics or olefins.

Fraenkel et al., U.S. Pat. No. 4,294,725, disclose a Fischer-Tropschcatalyst comprising a particulate synthetic zeolite incorporating atransition metal reduced in situ by a preselected vaporous reductantmetal and a method of making the catalyst. In the disclosed method formaking the catalyst, at least one reducible transition metal isincorporated by ion exchange into a particulate synthetic zeolitecatalyst support having ion-exchange properties, and the transitionmetal is then reduced with a vapor of at least one reductant metalhaving a reduction potential greater than the reduction potential of thetransition metal. In one specific embodiment disclosed, cadmium isdisclosed as a reducing metal which is present along with a transitionmetal in the final catalyst produced. Depending upon the conditionsemployed, saturated and unsaturated hydrocarbon products containing fromone to five carbon atoms and an unidentified oxygenated product wereproduced when a catalyst containing cobalt as the transition metal andcadmium as the reducing metal was employed.

Chu, U.S. Pat. No. 4,384,155, discloses a process for the conversion ofaromatic compounds, either alone or in admixture with a suitablealkylating agent, such as methanol or ethylene, to dialkylbenzenecompounds which are rich in the 1,4-dialkylbenzene isomer, in thepresence of a particular type of zeolite catalyst having asilica-to-alumina mole ratio of at least 12 and a constraint index ofabout 1-12, and containing a minor proportion of cadmium depositedthereon.

In addition, cadmium-containing catalysts have been employed in otherunrelated methods. For example, Wietzel et al., U.S. Pat. No. 1,562,480,disclose a method for synthesizing higher molecular weight organiccompounds containing oxygen by reacting an aliphatic alcohol with carbonmonoxide and optionally with hydrogen at a temperature of at least about400° C. and in the presence of the catalyst comprising bothhydrogenating and hydrating constituents. Suitable hydrogenatingconstituents are disclosed as including copper, silver, gold, tin, lead,antimony, bismuth, zinc, cadmium and thallium, and suitable hydratingconstitutents are disclosed as including titanium, zirconium, thorium,vanadium, niobium, manganese, cerium, lanthanum, tantalum, chromium,molybdenum, tungsten, uranium, didymium, glucinium and aluminum.

Perkins et al., U.S. Pat. No. 2,107,710, disclose a method forhydrolyzing a halohydrocarbon in the vapor phase and in the presence ofa catalyst comprising silica gell impregnated with one or more salts ofmetals belonging to the Groups IIB, IIIB, IVA or B, or VB of theperiodic system, for example, beryllium nitrate, magnesium sulfate, zincsulfate, cadmium nitrate, boron fluoride, aluminum chloride, stannouschloride, lead nitrate, titanium tetrachloride, antimony nitrate orbismuth chloride.

La Lande, U.S. Pat. No. 2,395,931, discloses a decolorizing adsorbent orcatalyst comprising a water-insoluble metal aluminate formed by thereaction in aqueous solution of an alkali metal aluminate and awater-soluble salt of a metal capable of forming a water-insoluble metalaluminate in the presence of a compound yielding ammonium ions. Suitablewater-soluble salts of metals capable of forming a water-insoluble metalaluminate include the chlorides or sulfates of magnesium, calcium, oraluminum, and soluble salts of strontium, barium, lead, copper, cadmium,iron, chromium, cobalt, nickel, manganese, thorium, cerium, beryllium,molybdenum, tin, titanium, zirconium, tungsten and vanadium. Thecatalyst is disclosed for use in decolorizing hydrocarbon oils.

Mecorney et al., U.S. Pat. No. 2,697,730, disclose a catalyst comprisingone or more metals, such as copper, silver, chromium, manganese, nickel,tungsten, cobalt, iron, cadmium, uranium, thorium, tin or zinc, eitherin the form of the elemental metals, their oxides, hydroxides, or salts,wherein the metal component is supported on activated alumina ordiatomaceous earth. The catalyst is disclosed for use in synthesizinghigher ketones.

Cislak et al., U.S. Pat. No. 2,744,904, disclose a process for preparingpyridine and 3-picoline by reacting acetylene, ammonia and methanol inthe presence of a catalyst comprising activated alumina impregnated withcadmium fluoride.

Finch et al., U.S. Pat. No. 2,763,696, disclose a method for reducingalpha- or beta-olefinic aldehydes or ketones to the corresponding alpha-or beta-unsaturated alcohols by direct hydrogenation of the aldehydes orketones in the vapor phase and in the presence of a catalyst comprisingelemental cadmium, its oxide, or a mixture thereof, and one or moreadditional metals known to have hydrogenating-dehydrogenatingcharacteristics, such as a heavy metal selected from the first, second,sixth or eighth groups of the Periodic Table of the Elements. Thesemetal components of the catalyst are disclosed as being employed eitherin the unsupported state or as supported on a suitable carrier, such assilica, alumina, kieselguhr or other diatomaceous earth material, pumiceor the like.

Pearson et al., U.S. Pat. No. 3,725,531, disclose a process whereinindustrial off-gases containing organic sulfur components are contactedwith an alumina base catalyst to convert these organic sulfur componentsto easily removable compounds, such as carbon dioxide and elementalsulfur. The catalyst employed comprises an alumina base support incombination with at least one metal selected from strontium, calcium,magnesium, zinc, cadmium, barium and molybdenum.

Eurlings et al., U.S. Pat. No. 3,862,055, disclose a method for thepreparation of a catalyst system having a catalytically-active componentof an oxide, metal or alloy of any one or more of copper, zinc, cadmium,nickel, cobalt, iron, manganese or magnesium, homogeneously dispersedover a solid particulate inorganic thermostable carrier material.Suitable inorganic thermostable materials, for use as the carrier, aredisclosed generally as including synthetic or mineral carrier materials,such as alumina or silica.

Eberly, U.S. Pat. No. 4,358,297, discloses a process wherein aparticulate sorbent mass of zeolite, which has been ion-exchanged withzinc or cadmium to provide pore size openings of at least about 5angstroms, is contacted with a moist hydrocarbon process stream whichcontains sulfur, sulfur compounds, and other contaminants, these beingadsorbed onto the particulate sorbent mass.

Mathe et al., U.S. Pat. No. 4,361,500, disclose a process for thepreparation of a supported metal catalyst containing at least one metalbelonging to Group A and optionally at least one metal belonging toGroup B, wherein Group A encompasses palladium, rhodium, ruthenium,platinum, iridium, osmium, silver, gold and cadmium, and Group Bencompasses zinc, mercury, germanium, tin, antimony and lead. Thispatent discloses that any of the known substances commonly used assupports for catalysts can be used as a support in the catalystdisclosed, and the following supports are specifically mentioned:activated carbons, aluminum oxides, silicon dioxides, aluminosilicatesand various molecular sieves, and barium sulfate. The catalyst isdisclosed for use in hydrogenation reactions.

OBJECTS OF THE INVENTION

It is a general object of the present invention to provide a catalystfor the direct production of gasoline boiling range aliphatic compoundsand aromatic compounds from less valuable materials.

More particularly, it is an object of the present invention to provide acatalyst for the direct production in a single step of branchedaliphatic hydrocarbons which boil in the gasoline range.

It is another object of the present invention to provide a catalyst forthe direct production in a single step of alkylated aromatic compounds.

It is a further object of the present invention to provide a catalystfor the direct and highly selective production in a single step ofp-xylene and pseudocumene.

It is a related object of the present invention to provide a catalysthaving improved activity maintenance for the direct production in asingle step of gasoline boiling range aliphatic compounds and aromaticcompounds from less valuable materials.

Other objects and advantages of the invention will become apparent uponreading the following detailed description and appended claims.

SUMMARY OF THE INVENTION

The present invention is a catalyst composition comprising a cadmiumcomponent, a thorium component and a support material having acidicproperties, wherein each of the cadmium component and the thoriumcomponent is in the form of the elemental metal, its oxide or salt or acombination thereof, wherein the cadmium component is present at aconcentration level in the range of from about 0.1 to about 20 weightpercent, calculated as cadmium oxide and based on the weight of thecatalyst, and wherein the thorium component is present at aconcentration in the range of from about 1 to about 25 weight percent,calculated as thorium oxide and based on the weight of the catalyst.

DETAILED DESCRIPTION

Catalysts of this invention comprise a cadmium component, a thoriumcomponent and a support material having acidic properties. The cadmiumcomponent can be present either as a component formed from a precursordeposited on the support or as a component formed from cadmium ionsexchanged into the support replacing exchangeable cations in thesupport. The cadmium component is in the form of elemental cadmium, itsoxide or salt or a combination thereof, and is present at aconcentration level in the range of from about 0.1 to about 20 weightpercent, calculated as cadmium oxide and based on the weight of thecatalyst. Preferably the cadmium component is present at a concentrationlevel of from about 1 to about 10 weight percent, calculated as cadmiumoxide and based on the weight of the catalyst. The cadmium component ispreferably in the form of cadmium oxide.

The thorium component has essentially no catalytic activity itself butserves to promote the catalytic activity of the cadmium component. Likethe cadmium component, the thorium component can be present either as acomponent deposited on the support or as a component of the supportformed from thorium ions exchanged into the support replacingexchangeable cations in the support. In addition, a thorium componentcan be a component of the support formed by admixture of a thoriumcomponent with an amorphous refractory inorganic oxide, such as alumina,silica or silica-alumina. The thorium component is in the form ofelemental thorium, its oxide or salt or a combination thereof, and ispresent at a concentration level in the range of from about 1 to about25 weight percent, calculated as thorium oxide and based on the weightof the catalyst. Preferably, the thorium component is present at aconcentration level of from about 3 to about 15 weight percent,calculated as thorium oxide and based on the weight of the catalyst. Thethorium component is preferably in the form of thorium oxide.

Any porous support material having acidic properties is suitable for usein the catalyst of this invention. Thus, suitable supports comprise anamorphous refractory inorganic oxide, a molecular sieve, a pillaredsmectite or vermiculite clay, or a combination thereof. Refractoryinorganic oxides having acidic properties typically comprise alumina,zirconia, titania, an oxide of a metal of the lanthanide series, anoxide of a metal of the actinide series, a combination thereof, or acombination thereof with silica or magnesia. The amorphous refractoryinorganic oxide can also include adjuvants, such as one or more oxidesof phosphorus or boron, or a halogen, such as chlorine or fluorine.

The support material of the catalyst of the present invention can alsocomprise a crystalline molecular sieve containing exchangeable cationsand can be in the unexchanged or cation-exchanged form. A suitablemolecular sieve comprises a crystalline aluminosilicate, crystallineborosilicate or a combination thereof. A suitable crystallinealuminosilicate includes chabazite, clinoptilolite, erionite, mordenite,zeolite A, zeolite L, zeolite X, zeolite Y, ultrastable large-porezeolite Y, zeolite omega, or a ZSM-type zeolite such as ZSM-5, ZSM-11,ZSM-12, ZSM-35, ZSM-38 or ZSM-48.

Mordenite-type crystalline aluminosilicates have been discussed in thepatent art, for example, in Kimberlin, U.S. Pat. No. 3,247,098; Benesiet al., U.S. Pat. No. 3,281,483; and Adams et al., in U.S. Pat. No.3,299,153. Those portions of each of these patents that are directed tomordenite-type aluminosilicates are specifically incorporated byreference herein. Synthetic mordenite-type crystalline aluminosilicates,designated as Zeolon, are available from the Norton Company ofWorcester, Mass.

One example of a crystalline molecular sieve that is suitable for use inthe support of the catalyst of the present invention is an unexchangedhigh sodium content, Y-type zeolitic crystalline alumino-silicate, suchas the sodium-Y molecular sieve, designated as Catalyst Base 30-200, andobtained from the Linde Division of Union Carbide Corporation.

Another example of a crystalline molecular sieve that can be employed inthe support of the catalyst of the present invention is ametal-exchanged, Y-type molecular sieve. Y-type, zeolitic molecularsieves are discussed in U.S. Pat. No. 3,130,007. The metal-exchanged,Y-type molecular sieve can be prepared by replacing the original cationassociated with the molecular sieve by a wide variety of other cationsaccording to techniques that are known in the art. Ion exchangetechniques have been disclosed in many patents, several of which areU.S. Pat. Nos. 3,140,249; 3,140,251; and 3,140,253. Specifically, amixture of rare earth metals can be exchanged into a Y-type zeoliticmolecular sieve, and such rare earth metal-exchanged, Y-type molecularsieve can be employed suitably in a support used in the catalyst of thepresent invention. Specific examples of suitable rare earth metals arecerium, lanthanum, and praesodymium. In one particularly preferredembodiment, cadmium ions are exchanged into a Y-type zeolitic molecularsieve, with the result being that the cadmium component of the catalystis a component of the catalyst support.

Ultrastable, large-pore, Y-type, zeolitic crystalline aluminosilicatematerial is described in U.S. Pat. Nos. 3,293,192 and 3,449,070. Each ofthese patents is specifically incorporated by reference herein. Bylarge-pore material is meant, a material that has pores which aresufficiently large to permit the passage thereinto of benzene moleculesand larger molecules and the passage therefrom of reaction products.

The ultrastable, large-pore, Y-type, zeolitic crystallinealuminosilicate material that is preferred for use in the support of thecatalyst of this invention exhibits a cubic unit cell dimension andhydroxyl infrared bands that distinguish it from other aluminosilicatematerials. The cubic unit cell dimension of the preferred ultrastable,large-pore, crystalline aluminosilicate is within the range of about24.20 angstroms to about 24.55 angstroms. The hydroxyl infrared bandsobtained with the preferred ultrastable, large-pore, crystallinealuminosilicate material are a band near 3,745 cm⁻¹ (3,745±5 cm⁻¹), aband near 3,695 cm⁻¹ (3,690±10 cm⁻¹), and a band near 3,625 cm⁻¹(3,610±15 cm⁻¹). The band near 3,745 cm⁻¹ may be found on many of thehydrogen-form and de-cationized aluminosilicate materials, but the bandnear 3,695 cm⁻¹ and the band near 3,625 cm⁻¹ are characteristic of thepreferred ultrastable, large-pore, Y-type, zeolitic crystallinealuminosilicate material that is used in the catalyst of the presentinvention. The ultrastable, large-pore, Y-type, zeolitic crystallinealuminosilicate material is also characterized by an alkaline metalcontent of less than 1%.

Other molecular sieve materials that are useful in the support of thecatalyst of the present invention are ZSM-type crystallinealuminosilicate molecular sieves. Suitable crystalline aluminosilicatesof this type typically have silica-to-alumina mole ratios of at leastabout 12:1 and pore diameters of at least 5 angstroms. A specificexample of a useful crystalline aluminosilicate zeolite of the ZSM-typeis ZSM-5, which is described in detail in U.S. Pat. No. 3,702,886. Othercrystalline aluminosilicate zeolites of the ZSM-type contemplatedaccording to the invention include, ZSM-11, which is described in detailin U.S. Pat. No. 3,709,979; ZSM-12, which is described in detail in U.S.Pat. No. 3,832,449; ZSM-35, which is described in U.S. Pat. No.4,016,245; and ZSM-38, which is described in detail in U.S. Pat. No.4,046,859. All of the aforesaid patents are incorporated herein byreference. A preferred crystalline aluminosilicate zeolite of theZSM-type is ZSM-5.

An additional molecular sieve that can be used in the catalyticcomposition of the present invention is a crystalline borosilicate,which is described in U.S. Pat. No. 4,269,813, which patent isspecifically incorporated herein by reference. A suitable crystallineborosilicate is a molecular sieve material having the followingcomposition in terms of mole ratios of oxides:

    0.9+/-0.2M.sub.2/n O:B.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O

wherein M is at least one cation having a valence of n, y is within therange of 4 to about 600, and z is within the range of 0 to about 160,and providing an X-ray pattern providing the following X-ray diffractionlines and assigned strengths:

    ______________________________________                                        d Angstroms   Assigned Strength                                               ______________________________________                                        11.2 ± 0.2 W-VS                                                            10.0 ± 0.2 W-MS                                                            5.97 ± 0.07                                                                              W-M                                                             3.82 ± 0.05                                                                              VS                                                              3.70 ± 0.05                                                                              MS                                                              3.62 ± 0.05                                                                              M-MS                                                            2.97 ± 0.02                                                                              W-M                                                             1.99 ± 0.02                                                                              VW-M                                                            ______________________________________                                    

M can be a cadmium ion, and thus the cadmium component can beincorporated into the crystalline borosilicate molecular sieve supportitself, in addition to or instead of being deposited on the surface ofthe crystalline borosilicate molecular sieve support.

Suitable methods for preparing the aforesaid crystalline borosilicatemolecular sieve are disclosed in Klotz, U.S. Pat. No. 4,269,813 and inHaddid, European patent application No. 82303246.1 which was publishedon Jan. 5, 1983.

Pillared smectite and vermiculite clays, which are also suitable for usein, or as, the support component of the catalyst of this invention, areoften referred in the literature as pillared interlayered clays andoccasionally as molecular sieves. The smectite clays comprisemontmorillonite, beidellite, montronite, volchonskoite, hectorite,saponite, stevensite, sauconite and pimelite. Some pillared smectite andvermiculite clay materials that are suitable for use in the support ofthe catalyst of this invention, and methods for preparing such clays,are disclosed in Vaughan et al., U.S. Pat. No. 4,176,090; Shabria etal., U.S. Pat. No. 4,216,188; Shabtai, U.S. Pat. No. 4,238,364;D'Aniello, U.S. Pat. No. 4,380,510; Pinnavaia, "Intercalated ClayCatalysts," Science, Vol. 220, pages 365-371 (Apr. 22, 1983) and Vaughanet al., "Preparation of Molecular Sieves Based on Pillared InterlayeredClays (PILC)," Fifth International Conference on Zeolites, pages 94-101and in the references cited therein. Preferably, a suitably pillaredsmectite clay comprises a multiplicity of cations interposed between themolecular layers of the clay and maintaining the spacing between themolecular layers in the range of from about 6 angstroms to about 10angstroms at a temperature of at least 300° C. in an air atmosphere forat least 2 hours.

Preferably, when the support comprises an aforesaid molecular sievematerial or an aforesaid pillared smectite or vermiculite clay materialor a combination thereof, the support also comprises an aforesaidamorphous refractory inorganic oxide. In such cases, the concentrationsof the amorphous inorganic oxide and of the molecular sieve materialand/or pillared smectite or vermiculite clay material are not critical.Preferably, the amorphous refractory inorganic oxide content is at leasthigh enough to be effective to give the support sufficient strength andintegrity so that the ultimate catalyst composition can be employedwithout appreciable damage to the catalyst. In such case, the totalconcentration of the molecular sieve material and/or pillared smectiteor vermiculite clay material in such mixture is preferably from 5 to 90weight percent, more preferably from 20 to 60 weight percent, based onthe weight of the support, which support is made up of the amorphousrefractory inorganic oxide and the molecular sieve material and/or thepillared smectite or vermiculite clay material.

Preferably, when the support comprises a mixture of a molecular sieveand/or pillared smectite or vermiculite clay and an amorphous refractoryinorganic oxide, the support is in the form of a dispersion of themolecular sieve component and/or pillared smectite or vermiculite claycomponent in a matrix of the amorphous refractory inorganic oxide. Suchdispersions can be prepared by well-known techniques, such as blendingthe molecular sieve component and/or pillared smectite or vermiculiteclay component, preferably in finely-divided form, into a sol, hydrosolor hydrogel of the inorganic oxide, and then adding a gelling medium,such as ammonium hydroxide, and stirring to produce a gel. Alternately,the molecular sieve component and/or pillared smectite or vermiculiteclay component is blended into a slurry of the amorphous inorganicoxide. In either case, the resulting mixture can be dried, shaped, ifdesired, and then calcined to form the final support component. A lesspreferred, but still suitable, method for preparing a suitabledispersion of the molecular sieve component and/or pillared smectite orvermiculite clay component in the inorganic oxide is to dry-blendparticles of each, preferably in finely-divided form, and then toconduct any desired shaping operations, such as pelletizing orextrusion; the resulting mixture is then calcined.

The catalysts of this invention can be prepared by impregnation of anaforesaid suitable support with at least one precursor of the cadmiumcomponent and of the thorium component. Any convenient conventionalimpregnation technique can be employed for this purpose. For example,when the support comprises an amorphous refractory inorganic oxide, asoluble cadmium compound and a soluble thorium compound can be added toa sol or gel of the amorphous refractory inorganic oxide. Thiscomposition is thoroughly blended, and the sol or gel mixture issubsequently co-gelled by the addition of a dilute ammonia solution. Theresulting co-gelled material is then dried and calcined. In anothermethod of preparation, the refractory inorganic oxide is gelled, dried,calcined, and cooled, and the resulting material is then impregnatedwith one or more solutions of a cadmium compound and of a thoriumcompound.

When the support comprises both an amorphous refractory inorganic oxideand a molecular sieve and/or a pillared smectite or vermiculite clay,numerous convenient impregnation techniques can also be employed. Forexample, finely-divided molecular sieve material and/or pillaredsmectite or vermiculite clay material can be stirred into a sol or gelof a refractory inorganic oxide, and at least one soluble compound ofcadmium and at least one soluble compound of thorium is added to the solor gel, followed by co-gelling of the sol or gel mixture by the additionof dilute ammonia. The resulting co-gelled material is then dried andcalcined.

In another method of preparation, finely-divided molecular sievematerial and/or pillared smectite or vermiculite clay material are mixedinto a sol or gel of a refractory inorganic oxide; the sol or gelmixture is co-gelled by the addition of dilute ammonia and the resultinggel is subsequently dried, calcined, cooled, and then impregnated with asolution or solutions of at least one soluble compound of cadmium and ofthorium. As an alternate method of preparation, a hydrogel of arefractory inorganic oxide is blended with finely-divided molecularsieve material and/or pillared smectite or vermiculite clay, and asolution or solutions of at least one soluble compound of cadmium and ofthorium is added to this blend, and the resulting mixture is thoroughlyblended. The blended mixture is then dried and calcined.

In still another method of preparation, the molecular sieve materialand/or pillared smectite or vermiculite clay material can be pulverizedinto a finely-divided state and then physically admixed with afinely-divided powder of the selected refractory inorganic oxidecomponent. After a thorough blending of the solid components, theresulting mixture can be co-pelleted, and impregnated with one or moresolutions of a cadmium compound and of a thorium compound.

It is, of course, also suitable to impregnate only one of the amorphousrefractory inorganic oxide, the molecular sieve material or pillaredsmectite or vermiculite clay material in the mixture, or to impregnateeach of the aforesaid amorphous inorganic oxide, molecular sievematerial and/or pillared smectite or vermiculite clay materialseparately, and then to blend the inorganic oxide and molecular sievematerial and/or pillared smectite or vermiculite clay material. Thus, itis contemplated that, if the catalyst of this invention comprises anamorphous refractory inorganic oxide and at least one of a molecularsieve material and a pillared smectite or vermiculite clay material, thecadmium component can be deposited on only one, only two, or all of thecomponents of the support. Similarly, in such cases, the thoriumcomponent can be present with the cadmium component on the samecomponent(s) of the support, or the cadmium component and thoriumcomponent can be on different components of the support.

It is preferred that, if the catalyst of this invention comprises asupport comprising a molecular sieve component or a pillared smectite orvermiculite clay component impregnated with the cadmium component andthe thorium component, the impregnation of the molecular sieve componentand pillared smectite or vermiculite clay component is conducted at a pHof at least about 2 in order to avoid substantial destruction of thecrystallinity of the aforesaid support component. More preferably, thepH of the impregnating solution(s) in such case is from about 2.5 toabout 6 in order to ensure substantial retention of the crystallinity ofthe aforesaid support component. Of course, the optimum pH range(s) ofthe impregnating solution(s) varies somewhat depending on the specificmolecular sieve component and pillared smectite or vermiculite claycomponent employed in the preparation of a given catalyst.

In each of the above preparations involving a molecular sieve material,the molecular sieve material employed can be either in its unexchangedform or in its ion-exchanged form. Preferably, the molecular sievematerial is one which has previously been cation-exchanged. A suitablecation-exchange procedure comprises making a slurry of the molecularsieve material in a solution of a cation, such as ammonium ions, whichis to be exchanged with the alkali metal in the molecular sievematerial, stirring the slurry at a temperature of about 100° C. for atleast about 2 hours to about one week, filtering the slurry, washing thefiltered solid with distilled water, and drying and calcining the solid.

It is also suitable to incorporate the precursor of the cadmiumcomponent and/or thorium component into the molecular sieve by cationexchange using a convenient, conventional ion exchange procedure, suchas the one described generally hereinabove. Thus, the cadmium componentand/or thorium component can be incorporated into the molecular sievesupport itself, in addition to or instead of being deposited on thesurface of the molecular sieve support.

Suitable conditions for drying the above-described impregnated orexchanged supports comprise a temperature in the range of from about 90°C. to about 200° C. and a drying time of from about 0.5 to about 30hours. Suitable calcination conditions in such methods comprise atemperature in the range of about 480° C. to about 760° C. and acalcination time of from about 2 to about 5 hours. Preferred drying andcalcination conditions are a temperature of about 120° C. for about 1-2hours and a temperature of about 538° C. for about 1-2 hours,respectively.

The catalysts of the present invention are suitable for use in a generalmethod comprising reacting hydrogen with a material selected from thegroup consisting of (a) carbon monoxide, (b) at least one of an alcoholcontaining from 1 to 6 carbon atoms and an olefin containing from 2-6carbon atoms, and (c) a mixture of an aromatic compound and at least oneof carbon monoxide and an alcohol containing from 1 to 6 carbon atoms.The conditions employed in this general method include a temperature inthe range of from about 300° C. to about 480° C. and a pressure in therange of from about 5 to about 150 kilograms per square centimeter.

For the reaction between carbon monoxide and hydrogen, the mole ratio ofcarbon monoxide-to-hydrogen is preferably in the range of from about1:10 to about 10:1, more preferably from about 2:1 to about 1:4. In suchcases, it is also preferred that the reaction is performed at atemperature in the range of from about 315° C. to about 425° C., at apressure of at least 35 kilograms per square centimeter, and with aspace velocity of from about 0.2 to about 5 moles of carbon monoxide pergram of catalyst per hour. In addition, the reaction between carbonmonoxide and hydrogen is performed in the presence of an aforesaidcatalyst of this invention whose support preferably comprises alumina,silica-alumina, cadmium-exchanged zeolite Y, rare earth-exchangedzeolite Y, ultrastable zeolite Y, pillared smectite or vermiculite clayor crystalline borosilicate molecular sieve and more preferablycomprises alumina, cadmium-exchanged zeolite Y, rare earth-exchangedzeolite Y, ultrastable zeolite Y, or pillared smectite or vermiculiteclay.

For the reaction between hydrogen and at least one of the aforesaidalcohol and the aforesaid olefin the alcohol preferably comprisesmethanol, ethanol, propanol or a combination thereof. When an alcohol isnot a reactant, the olefin preferably comprises propylene, butylene,amylene or a combination thereof. When an alcohol is a reactant, theolefin preferably comprises ethylene, propylene, butylene or acombination thereof. If an alcohol is a reactant, the mole ratio ofalcohol-to-hydrogen is preferably from about 1:10 to about 10:1, morepreferably from about 4:1 to about 1:4. If an olefin is a reactant, themole ratio of olefin-to-hydrogen is preferably from about 10:1 to about1:10, more preferably from about 4:1 to about 1:1. If both an alcoholand an olefin are reactants, the mole ratio of alcohol-to-olefin ispreferably from about 10:1 to about 1:10, more preferably from about 3:1to about 1:3. In such cases, it is also preferred that the reaction isperformed at a temperature in the range of from about 315° C. to aboutabout 425° C., at a pressure of at least about 10 kilograms per squarecentimeter, and with a space velocity of from about 0.01 to about 0.1moles of each of the alcohol and olefin that is present per gram ofcatalyst per hour. In addition, the reaction between hydrogen and atleast one of the alcohol and olefin, when an alcohol is present, ispreferably performed in the presence of a catalyst of this inventioncomprising a support comprising cadmium-exchanged zeolite Y, rareearth-exchanged zeolite Y, ultrastable zeolite Y, a pillared smectite orvemiculite clay, silica-alumina, crystalline borosilicate molecularsieve, or ZSM-5, and more preferably the support comprisessilica-alumina. Preferably, when an alcohol is not present, suchcatalyst comprises a support comprising cadmium-exchanged zeolite Y,rare earth-exchanged zeolite Y, ultrastable zeolite Y, crystallineborosilicate molecular sieve, or ZSM-5.

For the reaction between an aromatic compound, hydrogen and at least oneof carbon monoxide and an alcohol containing from 1 to 6 carbon atoms,the aromatic compound is preferably an unsubstituted or alkylatedbenzene or naphthalene. The alcohol preferably comprises methanol,ethanol, propanol or a combination thereof. The mole ratio of carbonmonoxide or alcohol or both-to-hydrogen is preferably in the range offrom about 1:10 to about 10:1, more preferably from about 4:1 to about1:4; and the mole ratio of carbon monoxide or alcohol orboth-to-aromatic compound is preferably from about 10:1 to about 1:10,more preferably from about 2:1 to about 1:10. Preferably, the spacevelocity of the aromatic compound is from about 0.02 to about 0.5 molesof the aromatic compound per gram of catalyst per hour. It is alsopreferred that the reaction between the aromatic compound, hydrogen andat least one of carbon monoxide and an alcohol containing from 1 to 6carbon atoms is performed at a temperature in the range of from about315° C. to about 450° C., at a pressure in the range of from about 30 toabout 100 kilograms per square centimeter. In addition, the reactionbetween the aromatic compound, hydrogen and at least one of carbonmonoxide and an alcohol containing from 1 to 6 carbon atoms ispreferably performed in the presence of a catalyst of this inventioncomprising a support comprising cadmium-exchanged zeolite Y, rareearth-exchanged zeolite Y, ultrastable zeolite Y, a pillared smectite orvermiculite clay, silica-alumina, crystalline borosilicate molecularsieve, or ZSM-5. More preferably, the catalyst support comprisescrystalline borosilicate molecular sieve or ZSM-5, and in such cases,the feed is preferably benzene or toluene, and at least one of p-xyleneand pseudocumene is produced. Preferably carbon monoxide is a reactant.

The present invention will be more clearly understood from the followingspecific examples.

EXAMPLE 1

A solution containing 3 grams of Cd(NO₃)₂.4H₂ O and 7.84 grams ofTh(NO₃)₄.4H₂ O in 9 milliliters of water was combined and blended for 1hour with 23.75 grams of gamma alumina (from Continental Oil Company anddesignated Catapal) having a pore volume of 0.65 cubic centimeter pergram, a surface area of 200 square meters per gram, an average porediameter of 130 angstroms, and a particle size of 0.16 centimeter. Theblend was then dried at 120° C. for 1 hour and calcined at 540° C. inair for 1 hour. The resulting catalyst contained 5 weight percent ofcadmium oxide and 15 weight percent of thorium oxide, based on theweight of the catalyst.

EXAMPLE 2

35.4 grams of Th(NO₃)₄.4H₂ O was dissolved in water and blended with555.7 grams of an alumina sol containing about 9 weight percent ofalumina. 25 milliliters of an aqueous solution containing about 28weight percent of ammonium hydroxide was added to the resulting blend togel the sol. The resulting gel was dried at 120° C. overnight and thencalcined at 540° C. in air for 4 hours. The resulting composite materialcontained 25 weight percent of thorium oxide. A solution containing 6grams of Cd(NO₃)₂.4H₂ O in 10 milliliters of water was then blended with18 grams of the composite and the procedure of Example 1 was followed.The resulting catalyst contained 10 weight percent of cadmium oxide and22.5 weight percent of thorium oxide, based on the weight of thecatalyst.

EXAMPLE 3

691 grams of an alumina sol containing about 10 weight percent ofalumina was blended with 3000 grams of a silica-alumina sol containingabout 5.24 weight percent of silica-alumina of which about 72 weightpercent was silica and about 28 weight percent was alumina. 400milliliters of an aqueous solution containing about 50 weight percent ofammonium hydroxide was blended with the aforesaid blend until a pastyconsistency was achieved.

This procedure was repeated twice so that 3 batches of the paste werecollected. The 3 batches were then combined, and 1 liter of theaforesaid aqueous ammonium hydroxide solution was added to the resultingcombination. After standing for 24 hours, the resulting mixture wasdried in air at 120° C. for several days, ground and sieved to pass a100 mesh sieve (U.S. Series). The resulting solid was mulled with waterand a small amount of PHF alumina, and was then extruded to a diameterof 0.16 centimeter. The extrudate was dried overnight in air at 120° C.and then calcined in air at 538° C. for 4 hours. The resulting materialcontained 50 weight percent of alumina and 50 weight percent of silica,and had a pore volume of 0.48 cubic centimeter per gram, a surface areaof 227 square meters per gram and an average pore diameter of 110 Å.

The procedure of Example 1 was then repeated except that a solutioncontaining 5.4 grams of Cd(NO₃)₂.4H₂ O and 7.84 grams of Th(NO₃)₂.4H₂ Oin water was blended with 19 grams of the resulting silica-aluminacontaining 50 weight percent of silica and 50 weight percent of alumina.The resulting catalyst contained 9 weight percent of cadmium oxide and15 weight percent of thorium oxide, based on the weight of the catalyst.

EXAMPLE 4

The procedure of Example 3 was repeated, except that a solutioncontaining 3 grams of Cd(NO₃)₂.4H₂ O and 6.27 grams of Th(NO₃)₂.4H₂ Owas blended with 16 grams of the type of the silica-alumina compositecontaining 50 weight percent of silica and 50 weight percent of aluminaand used in Example 3. The resulting catalyst contained 5 weight percentof cadmium oxide and 15 weight percent of thorium oxide, based on theweight of the catalyst.

EXAMPLE 5

3000 grams of zeolite Y in the sodium form (from Union CarbideCorporation and designated LZ-Y52) was slurried in 8 liters of water,and 4000 grams of a solution of a commercially available mixture of rareearth chlorides was added to the slurry. The resulting slurry wasstirred and heated at reflux for 1 hour. The solids were allowed tosettle overnight and the supernatant liquid was siphoned off. Theresulting solids were exchanged a second time with 4 kilograms of themixture of rare earth chlorides in 2 liters of water, and the aforesaidstirring, refluxing, settling and siphoning steps were repeated. Theresulting solids were exchanged a third time with 4 kilograms of themixture of rare earth chlorides in 6 liters of water, and the aforesaidstirring, refluxing, settling and siphoning steps were repeated. Theresulting solids were washed each of 4 times with 6 liters of water,dried overnight at 120° C. and calcined for 4 hours at about 780° C.

The aforesaid triple exchange was repeated, except using instead in eachexchange solution 2000 grams of the mixture of rare earth chlorides andadditionally in the third exchange solution 400 grams of ammoniumnitrate. The stirring, refluxing, settling, siphoning, washing anddrying steps were as described for the first triple exchange.

The aforesaid triple exchange was repeated a second time, using the samesteps and conditions employed in the aforesaid second triple exchange.

The final rare earth-exchanged zeolite Y demonstrated 92 percentcrystallinity and contained 0.241 weight percent of sodium, 2.4 weightpercent of lanthanum, 8.6 weight percent of cerium, 2.9 weight percentof neodymium, 0.20 weight percent of thorium, 1.1 weight percent ofyttrium, 6.6 weight percent of aluminum and 24.8 weight percent ofsilicon.

120.0 grams of the resulting rare earth-exchanged zeolite Y was groundto pass a 100 mesh sieve (U.S. Series) and mixed with approximately 400milliliters of water. The resulting mixture was blended with 2800 gramsof an alumina sol containing about 10 weight percent of alumina. 300milliliters of an aqueous solution of ammonium hydroxide containing 50weight percent of ammonium hydroxide was added rapidly to the resultingblend, with stirring, to gel the mixture of the rare earth-exchangedzeolite Y and alumina. The gelled material was dried at 120° C. for 40hours. The dried material was then ground to pass a 100 mesh sieve (U.S.Series), mulled with water and extruded to a diameter of 0.2 centimeter.The extrudate was dried at 120° C. in air for 6 hours and then calcinedat 540° C. in air for 6 hours. The resulting composition contained 30weight percent of rare earth-exchanged zeolite Y and 70 weight percentof alumina.

EXAMPLE 6

A solution containing 3 grams of Cd(NO₃)₂.4H₂ O and 7.84 grams ofTh(NO₃)₄.4H₂ O in 8 milliliters of water was combined and blended for 1hour with 20 grams of the final rare earth-exchanged zeolite Y producedin Example 5. The blend was then dried at 120° C. for 1 hour andcalcined at 540° C. in air for 1 hour. The resulting catalyst contained5 weight percent of cadmium oxide and 15 weight percent of thoriumoxide, based on the weight of the catalyst.

EXAMPLE 7

25 grams of rare earth-exchanged zeolite Y prepared as in Example 5 wasground to pass a 100 mesh sieve (U.S. Series) and suspended in water.The resulting suspension was blended with 275 grams of an alumina solcontaining about 9 weight percent of alumina. 13 milliliters of anaqueous solution containing 28 weight percent of ammonium hydroxide wasthen added rapidly, with stirring, to the resulting blend to gel themixture of the rare earth-exchanged zeolite Y and alumina. The resultinggelled material was dried overnight at 120° C. and calcined at 540° C.in air for 1 hour. The resulting composition contained 50 weight percentof rare earth-exchanged zeolite Y and 50 weight percent of alumina.

A solution containing 13.4 grams of Cd(NO₃)₂.4H₂ O and 17.5 grams ofTh(NO₃)₄.4H₂ O in 16 milliliters of water was combined and blended for 1hour with 44.7 grams of the aforesaid composition containing 50 weightpercent of rare earth-exchanged zeolite Y and 50 weight percent ofalumina. The blend was then dried at 120° C. for several hours andcalcined at 540° C. in air for 4 hours. The resulting catalyst contained5 weight percent of cadmium oxide and 15 weight percent of thoriumoxide, based on the weight of the catalyst.

EXAMPLE 8

90 grams of H-Zeolon (Zeolon 200 from the Norton Company) was ground topass a 100 mesh sieve (U.S. Series), and the resulting particles wereslurried with distilled water. The resulting slurry was blended with3600 grams of an alumina sol containing about 10 weight percent ofalumina. 215 milliliters of an aqueous solution containing about 50weight percent of ammonium hydroxide was then added to gel the mixtureof H-Zeolon and alumina. The resulting gel was dried over a period ofseveral days at 120° C. in air. The dried particles were ground to passa 100 mesh sieve (U.S. Series), mulled with water and extruded to adiameter of 0.2 centimeter. The extrudate was dried at 120° C. for 2hours in air and calcined at 540° C. for 7 hours in air. The resultingcomposition contained 20 weight percent of H-Zeolon and 80 weightpercent of alumina.

A solution containing 3 grams of Cd(NO₃)₂.4H₂ O and 7.84 grams ofTh(NO₃)₄.4H₂ O in 8 milliliters of water was combined and blended with20 grams of the aforesaid composition containing 20 weight percent ofH-Zeolon in alumina. The blend was then dried at 120° C. for 1 hour andcalcined at 540° C. in air for 1 hour. The resulting catalyst contained5 weight percent of cadmium oxide and 15 weight percent of thoriumoxide, based on the weight of the catalyst.

EXAMPLE 9

180 grams of crystalline borosilicate (obtained from Amoco ChemicalsCorporation and designated HAMS-1B) was suspended in sufficient water toform a sauce-like consistency and combined and blended with 3600 gramsof an alumina sol containing about 10 weight percent of alumina. 400milliliters of an aqueous solution containing about 50 weight percent ofammonium hydroxide was added to the blend to gel the mixture ofcrystalline borosilicate and alumina. The resulting gel was dried at120° C. in air overnight. The dried particles were ground to pass a 100mesh sieve (U.S. Series), mulled with water, extruded to a diameter of0.32 centimeter, dried at 120° C. overnight and calcined at 540° C. inair overnight. The resulting composition contained 40 weight percent ofcrystalline borosilicate HAMS-1B and 60 weight percent of alumina.

A solution containing 3 grams of Cd(NO₃)₂.4H₂ O and 7.84 grams ofTh(NO₃)₄.4H₂ O in 8 milliliters of water was combined and blended for 1hour with 20 grams of the aforesaid composition containing 40 weightpercent of HAMS-1B. The blend was then dried at 120° C. for 1 hour andcalcined at 540° C. in air for 1 hour. The resulting catalyst contained5 weight percent of cadmium oxide and 15 weight percent of thoriumoxide, based on the weight of the catalyst.

EXAMPLE 10

ZSM-5 having a mole ratio for silica-to-alumina of 30:1 was prepared bydissolving 208 grams of tetrapropylammonium bromide and 42 grams ofsodium aluminate in 400 milliliters of an aqueous solution containing37.2 grams of sodium hydroxide. Then 1077 grams of Ludox (a silica sol)and sufficient water to bring the total solution volume to 18 literswere blended with the aforesaid aqueous solution. The blend was thenheated at about 150° C. for 5 days in an autoclave. Thereafter the solidwas washed with hot water 3 times, dried overnight at about 120° C. andthen calcined at about 540° C.

350 grams of 30:1 ZSM-5 was ground to pass a 100 mesh sieve (U.S.Series) and then suspended in water. The resulting suspension wascombined with 2265.4 grams of an alumina sol containing about 10 weightpercent of alumina. 400 milliliters of an aqueous solution containingabout 14 weight percent of ammonium hydroxide was added to the resultingmixture to form a gel. The resulting gel was dried at 120° C. in air.The dried material was then ground to pass a 100 mesh sieve (U.S.Series) and extruded to a diameter of 0.32 centimeter. The extrudate wasdried at 120° C. and then calcined at 540° C. for 20 hours. Theresulting composition contained 60 weight percent of ZSM-5 and 40 weightpercent of alumina.

A solution containing 3 grams of Cd(NO₃)₂.4H₂ O and 7.84 grams ofTh(NO₃)₄.4H₂ O in 8 milliliters of water was combined and blended for 1hour with 20 grams of the aforesaid composition containing 60 weightpercent of ZSM-5 and 40 weight percent of alumina. The blend was thendried at 120° C. for 1 hour and calcined at 540° C. in air for 1 hour.The resulting catalyst contained 5 weight percent of cadmium oxide and15 weight percent of thorium oxide, based on the weight of the catalyst.

EXAMPLE 11

90 grams of ultrastable zeolite Y crystalline aluminosilicate wasslurried in water, and the slurry was combined and blended with 3600grams of an alumina sol containing about 10 weight percent of alumina.250 grams of an aqueous solution containing about 28 weight percent ofammonium hydroxide was added to gel the resulting mixture. The resultinggel was dried at 120° C. and then ground to pass a 100 mesh sieve (U.S.Series). The ground material was next mulled with water and extruded toa 0.16 centimeter diameter. The extrudate was dried overnight at 120° C.and calcined at 540° C. for 7 hours. The resulting composition contained30 weight percent of ultrastable zeolite Y and 70 weight percent ofalumina.

A solution containing 3 grams of Cd(NO₃)₂ "4H₂ O and 7.84 grams ofTh(NO₃)₂ "4H₂ O in 8 grams of water was blended with the aforesaidcomposition containing ultrastable zeolite Y and alumina. The resultingmixture was dried at 120° C. and then calcined at 540° C. for 1 hour.The resulting catalyst contained 5 weight percent of cadmium oxide and15 weight percent of thorium oxide, based on the weight of the catalyst.

EXAMPLES 12-29

Examples 12-29 were performed using a 300-cubic centimeter, back-mixedreactor in which the flow of each gaseous and liquid reactant employedinto the reactor was controlled individually. To start a run in each ofExamples 12-29, 10 grams of the particular catalyst used was loaded intothe reactor, and the reactor was closed. The pressure of the reactor wasthen raised to the desired level by introducing the gaseous reactant(s)employed. The temperature of the reactor was then raised to the desiredlevel, at which point any liquid reactant(s) employed was thenintroduced into the reactor where it contacted the catalyst and gaseousreactant(s). Products and unreacted reactants passed continuously out ofthe reactor.

The catalyst, temperature, pressure and feed rates of each reactantemployed in Examples 12-29 are presented in Tables 1-4. The feed rate ofeach liquid reactant is presented in Tables 1-4 in terms of its liquidhourly space velocity--that is, the feed rate of the liquid in cubiccentimeters per hour divided by the number (10) of grams of catalyst inthe reactor. The combined feed rate of the gaseous reactant(s) ispresented in Tables 1-4 in terms of the gas weight hourly spacevelocity--that is, the combined gaseous feed rate in cubic centimetersper hour divided by weight of catalyst in the reactor. When both carbonmonoxide and hydrogen were employed, they were introduced into thereactor at a mole ratio of carbon monoxide-to-hydrogen of 1:2. A mixtureof hydrogen and carbon monoxide was employed in Examples 12, 14, 19, 20,22, 24, 26, 28 and 29. Hydrogen was the only gas employed in Examples13, 15-18, 21, 23, 25 and 27. Methanol was the liquid feed in Examples13, 15-18, 21, 23, 25 and 27. Toluene is the aromatic liquid feed inExamples 28 and 29.

The compositions of the organic products for each of Examples 12-29 arealso indicated in Tables 1-4. In Tables 1-4, the concentrations ofbutylenes are not reported separately but are included in theconcentrations of i-C₅ H₁₂ and n-C₅ H₁₂. In all of the tables, Tindicates trace amounts.

                  TABLE 1                                                         ______________________________________                                        Example No.       12     13     14   15   16                                  ______________________________________                                        Catalyst from     3      4      11   11   11                                  Example No.                                                                   Temperature (°C.)                                                                        432    432    399  399  399                                 Pressure (atm.)   34     34     34   34   68                                  Gas feed rate     2000   900    1100 1400 1400                                (cc./hr./gm.)                                                                 Liquid feed rate  --     1.0    --   1.0  1.0                                 (cc./hr./gm.)                                                                 Product Composition (Wt. %)                                                   CH.sub.4          75     7      27   12   27                                  C.sub.2 H.sub.6 --C.sub.2 H.sub.4                                                               9      11     6    4    3                                   C.sub.3 H.sub.6   4      5      4    3    3                                   C.sub.3 H.sub.8   1      8      6    5    3                                   i-C.sub.4 H.sub.10                                                                              3      9      16   25   18                                  n-C.sub.4 H.sub.10                                                                              1      2      2    2    2                                   i-C.sub.5 H.sub.12                                                                              3      6      13   17   18                                  n-C.sub.5 H.sub.12                                                                              T      T      1    1    1                                   i-C.sub.6 H.sub.14                                                                              2      5      9    11   6                                   n-C.sub.6 H.sub.14                                                                              T      1      1    1    1                                   C.sub.6.sup.+     2      30     15   12   12                                  DME               --     16     --   7    6                                   ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Example No.       17     18     19   20   21                                  ______________________________________                                        Catalyst from     11     11     6    6    6                                   Example No.                                                                   Temperature (°C.)                                                                        427    456    399  399  371                                 Pressure (atm.)   34     34     68   34   34                                  Gas feed rate     1400   1400   1700 1700 1100                                (cc./hr./gm.)                                                                 Liquid feed rate  1.0    1.0    --   --   1.0                                 (cc./hr./gm.)                                                                 Product Composition (Wt. %)                                                   CH.sub.4          18     21     16   12   6                                   C.sub.2 H.sub.6 --C.sub.2 H.sub.4                                                               7      8      8    8    3                                   C.sub.3 H.sub.8   5      5      5    3    2                                   C.sub.3 H.sub.6   5      6      3    5    3                                   i-C.sub.4 H.sub.10                                                                              22     18     18   17   36                                  n-C.sub.4 H.sub.10                                                                              3      3      3    2    2                                   i-C.sub.5 H.sub.12                                                                              16     15     17   13   19                                  n-C.sub.5 H.sub.12                                                                              2      2      1    1    1                                   i-C.sub.6 H.sub.14                                                                              10     9      10   9    11                                  n-C.sub.6 H.sub.14                                                                              1      1      --   --   --                                  C.sub.6.sup.+     9      10     19   30   15                                  DME               2      2      --   --   5                                   ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Example No.   22     23     24   25    26   27                                ______________________________________                                        Catalyst from 9      9      10   10    8    8                                 Example No.                                                                   Temperature (°C.)                                                                    399    399    399  399   399  399                               Pressure (atm.)                                                                             34     34     34   34    34   34                                Gas feed rate 1850   1400   2000 1400  1000 1400                              (cc./hr./gm.)                                                                 Liquid feed rate                                                                            --     1.0    --   1.0   --   1.0                               (cc./hr./gm.)                                                                 Product Composition                                                           (Wt. %)                                                                       CH.sub.4      88     20     85   23    60   48                                C.sub.2 H.sub.6 --C.sub.2 H.sub.4                                                           10     2      13   5     7    4                                 C.sub.3 H.sub.8                                                                             --     4      1    8     19   22                                C.sub.3 H.sub.6                                                                             --     3      --   1     --   --                                i-C.sub.4 H.sub.10                                                                          --     12     --   13    2    2                                 n-C.sub.4 H.sub.10                                                                          --     2      --   2     3    5                                 i-C.sub.5 H.sub.12                                                                          --     16     --   15    2    2                                 n-C.sub.5 H.sub.12                                                                          --     7      --   1     --   --                                i-C.sub.6 H.sub.14                                                                          --     20     --   13    1    2                                 n-C.sub.6 H.sub.14                                                                          --     1      --   --    --   --                                C.sub.6.sup.+ --     8      1    17    6    15                                DME           --     5      --   2     --   --                                ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Example No.         28      29                                                ______________________________________                                        Catalyst from       9       9                                                 Example No.                                                                   Temperature (°C.)                                                                          399     405                                               Pressure (atm.)     34      68                                                Gas feed rate       850     1550                                              (cc./hr./gm.)                                                                 Liquid feed rate    1.0.sup.1                                                                             1.0.sup.1                                         (cc./hr./gm.)                                                                 Aromatic            25      60                                                conversion (%)                                                                Product Composition (Wt. %)                                                   C.sub.1 -C.sub.6    6       3                                                 Benzene             12      2                                                 Toluene             --      --                                                Ethylbenzene        --      --                                                m/p-xylene          45      30                                                o-xylene            16      12                                                1,3,5-trimethylbenzene                                                                            --      2                                                 pseudocumene        8       23                                                1,2,3-trimethylbenzene                                                                            --      1                                                 tetramethylbenzene  2       16                                                Other aromatics     11      11                                                ______________________________________                                         Footnotes                                                                     .sup.1 Toluene                                                           

EXAMPLES 30-45

Examples 30-45 were performed in a flow pipe reactor having a diameterof 0.95 centimeter and 63.5 centimeters long and containing a bed ofabout 10 grams of catalyst. A premixed mixture of carbon monoxide andhydrogen was introduced through one end of the pipe reactor, and reactoreffluent was withdrawn from the other end of the reactor. The gasintroduced to the reactor was used to pressure the reactor to thedesired level.

The catalyst, temperature, pressure and feed rates of each reactantemployed in Examples 30-45 are presented in Tables 5-8. The combinedfeed rate of the gaseous reactant(s) is presented in Tables 5-8 in termsof the gas weight hourly space velocity--that is, the combined gaseousfeed rate in cubic centimeters per hour divided by weight of catalyst inthe reactor. Carbon monoxide and hydrogen were introduced into thereactor at a mole ratio of carbon monoxide-to-hydrogen of 1:2 in allcases except in Example 45 where the mole ratio was 1:1.

The compositions of the organic products for each of Examples 30-45 arealso indicated in Tables 5-8.

                  TABLE 5                                                         ______________________________________                                        Example No.      30        31      32                                         ______________________________________                                        Catalyst from    11        11      11                                         Example No.                                                                   Temperature (°C.)                                                                       316       344     371                                        Pressure (atm.)  34        34      34                                         Gas feed rate    1400      1400    1400                                       (cc./hr./gm.)                                                                 CO conversion (%)                                                                              15        20      24                                         % CO converted to                                                                              35        48      60                                         CO.sub.2 and H.sub.2                                                          Product Composition (Wt. %)                                                   CH.sub.4         --        10      32                                         i-C.sub.4 H.sub.10                                                                             --         6      21                                         i-C.sub.5 H.sub.12                                                                             --        --      13                                         Methanol         --         7       6                                         DME              100       78      28                                         ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Example No.      33        34      35                                         ______________________________________                                        Catalyst from     6         6       6                                         Example No.                                                                   Temperature (°C.)                                                                       357       375     399                                        Pressure (atm.)  34        34      34                                         Gas feed rate    1500      1500    1500                                       (cc./hr./gm.)                                                                 CO conversion (%)                                                                              46        50      50                                         % CO converted to                                                                              54        59      58                                         CO.sub.2 and H.sub.2                                                          Product Composition (Wt. %)                                                   CH.sub.4         22        42      57                                         C.sub.2 H.sub.6   4        --      --                                         C.sub.3 H.sub.6  16        19      13                                         C.sub.3 H.sub.8   5        --      --                                         i-C.sub.4 H.sub.10                                                                             33        23      17                                         n-C.sub.4 H.sub.10                                                                              4         5       4                                         i-C.sub.5 H.sub.12                                                                             15        11       9                                         ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Example No.       36     37     38   39   40                                  ______________________________________                                        Catalyst from     1      1      2    2    2                                   Example No.                                                                   Temperature (°C.)                                                                        316    371    344  371  404                                 Pressure (atm.)   34     34     34   34   34                                  Gas feed rate     1800   1350   1500 1500 1500                                (cc./hr./gm.)                                                                 CO conversion (%) 27     33     24   23   21                                  % CO converted to 35     41     43   46   49                                  CO.sub.2 and H.sub.2                                                          Product Composition (Wt. %)                                                   CH.sub.4          8      21     13   44   84                                  CH.sub.3 OH       9      11     7    7    6                                   (CH.sub.3).sub.2 O                                                                              83     68     80   49   10                                  ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Example No.       41     42     43   44   45                                  ______________________________________                                        Day No.           2      7      14   22   27                                  Catalyst from     7      7      7    7    7                                   Example No.                                                                   Temperature (°C.)                                                                        371    379    381  381  388                                 Pressure (atm.)   34     34     34   34   34                                  Gas feed rate     1650   1650   1700 1800 1700                                (cc./hr./gm.)                                                                 CO conversion     29     27     24   18   18                                  % CO converted to 65     52     49   52   43                                  CO.sub.2 and H.sub.2                                                          Product Composition (Wt. %)                                                   CH.sub.4          39     31     28   22   28                                  C.sub.3 H.sub.6   2      1      1    --   --                                  C.sub.3 H.sub.8   15     14     14   15   14                                  i-C.sub.4 H.sub.10                                                                              28     33     40   46   44                                  n-C.sub.4 H.sub.10                                                                              4      8      4    --   --                                  i-C.sub.5 H.sub.12                                                                              12     13     13   17   14                                  ______________________________________                                    

Examples 12, 14, 19, 20, 22, 24, 26 and 30-45 involve the reactionbetween carbon monoxide and hydrogen. The results of these examplesillustrate both a high selectivity for the production of branchedhydrocarbons in this reaction relative to the production of unbranchedhydrocarbons having the same number of carbon atoms, and the productionof C₅ + and C₆ +, which are primarily mixtures of branched hydrocarbonscontaining at least 6 carbon atoms and at least 7 carbon atoms,respectively. Comparison of the results of Examples 19 and 20 indicatesthat an increase in the reaction pressure causes an increase in theyield of methane and a decrease in the yield of C₆ + material.

Comparison of the results of Examples 30-32 indicates that increases inthe reaction temperature result in increases in the degree of carbonmonoxide conversion, increases in the methane yield, and increases inthe relative yields of branched hydrocarbons-to-unbranched hydrocarbons.Furthermore, Examples 30-32 illustrate that at low reaction temperaturesdimethylether (DME) is the only organic product, but that at highertemperatures, hydrocarbons and methanol are produced. Comparison of theresults of Examples 33-35 and 38-40 indicate that increases in thereaction temperature result in increases in the carbon monoxideconversion and in the methane yield and in decreases in the yields ofisopentane, C₅ +, methanol and dimethylether.

Examples 41-45 illustrate that catalytic activity in this reaction ismaintained over a test period spanning 27 days. In Examples 41-45, itwas necessary to increase the reaction temperature only about 17° C. inorder to partially offset the decrease of catalytic activity. Bycontrast, a catalyst otherwise the same except not containing a cadmiumcomponent does not catalyze this reaction under substantially the samereaction conditions.

Examples 13, 15-18, 21, 23, 25 and 27 involve reactions between hydrogenand at least one of an alcohol containing from 1 to 6 carbon atoms andan olefin containing from 2 to 6 carbon atoms. Comparison of the resultsof Examples 23, 25 and 26 with the results of Examples 22, 24 and 26,respectively, illustrates that relatively smaller amounts of methane andrelatively greater amounts of C₆ + are produced in the reaction betweenhydrogen and the alcohol and/or olefin than in the reaction betweenhydrogen and carbon monoxide.

Comparison of the results of Examples 15-18 illustrates that increasesin the reaction pressure, or temperature, result in increases in therelative yield of methane and in decreases in the relative yields ofbranched hydrocarbons.

Examples 28 and 29 involve the reaction between an aromatic compound,hydrogen and at least one of carbon monoxide and an alcohol containingfrom 1 to 6 carbon atoms. In such cases, products that are methylatedderivatives--other than disproportionation products--of the aromaticcomponent of the feed were formed. Examples 28 and 29 illustrate thatincreases in reaction temperature and pressure afford increasedconversion of the aromatic feed component, and increased overall yieldsof polymethylated products, such as pseudocumene, tetramethylbenzenesand other aromatics. Comparison of the results of Examples 28 and 29illustrates that the use of higher reaction pressures results in greateraromatic conversion and a greater total yield of the more highlymethylated products.

From the above description, it is apparent that the objects of thepresent invention have been achieved. While only certain have been setforth, alternative embodiments and various modifications will beapparent from the above description to those skilled in the art. Theseand other alternatives are considered equivalents and within the spiritand scope of the present invention.

Having described the invention, what is claimed is:
 1. A catalystcomposition comprising a cadmium component, a thorium component and asupport material having acidic properties, wherein each of the cadmiumcomponent and the thorium component is in the form of the elementalmetal, its oxide or salt or a combination thereof, wherein the cadmiumcomponent is present at a concentration level in the range of from about0.1 to about 20 weight percent, calculated as cadmium oxide and based onthe weight of the catalyst, and wherein the thorium component is presentat a concentration in the range of from about 1 to about 25 weightpercent, calculated as thorium oxide and based on the weight of thecatalyst.
 2. The catalyst composition of claim 1 wherein the cadmiumcomponent is in the form of cadmium oxide.
 3. The catalyst compositionof claim 1 wherein the cadmium component is present at a concentrationlevel in the range of from about 1 to about 10 weight percent,calculated as cadmium oxide and based on the weight of the catalyst. 4.The catalyst composition of claim 1 wherein the thorium component is inthe form of thorium oxide.
 5. The catalyst composition of claim 1wherein the support comprises a refractory inorganic oxide, a molecularsieve, a pillared smectite or vermiculite clay or a combination thereof.6. The catalyst composition of claim 5 wherein the refractory inorganicoxide comprises alumina, zirconia, titania, an oxide of a metal of thelanthanide series, a combination thereof, or a combination thereof withsilica or magnesia.
 7. The catalyst composition of claim 5 wherein themolecular sieve comprises a crystalline aluminosilicate, crystallineborosilicate, or mixture thereof, in the unexchanged or cation-exchangedform.
 8. The catalyst composition of claim 7 wherein the crystallinealuminosilicate comprises chabazite, mordenite, erionite,clinoptilolite, zeolite A, zeolite L, zeolite X, zeolite Y, ultrastablezeolite Y, zeolite omega, ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38 orZSM-48.
 9. The catalyst composition of claim 7 wherein the crystallinealuminosilicate is in the hydrogen- or rare earth-exchanged form. 10.The catalyst composition of claim 7 wherein the crystalline borosilicatemolecular sieve comprises a molecular sieve material having thefollowing composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O

wherein M is at least one cation having a valence of n, y is between 4and about 600, and z is between 0 and about 160, and providing an X-raydiffraction pattern comprising the following X-ray diffraction lines andassigned strengths:

    ______________________________________                                        ˜d (Å)                                                                            Assigned Strength                                               ______________________________________                                        11.2 ± 0.2 W-VS                                                            10.0 ± 0.2 W-MS                                                            5.97 ± 0.07                                                                              W-M                                                             3.82 ± 0.05                                                                              VS                                                              3.70 ± 0.05                                                                              MS                                                              3.62 ± 0.05                                                                              M-MS                                                            2.97 ± 0.02                                                                              W-M                                                             1.99 ± 0.02                                                                              VW-M                                                            ______________________________________                                    


11. The catalyst composition of claim 5 wherein the pillared smectite orvermiculite clay comprises a multiplicity of cations interposed betweenthe molecular layers of the clay and maintaining the spacing between themolecular layers in the range of from about 6 angstroms to about 10angstroms at a temperature of at least 300° C. in an air atmosphere forat least 2 hours.
 12. The catalyst composition of claim 5 wherein thesupport comprises from about 20 to about 95 weight percent of anaforesaid refractory inorganic oxide and from about 5 to about 80 weightpercent of an aforesaid molecular sieve or pillared smectite orvermiculite clay.